Hyperthermophilic redox chemistry: a re-evaluation

The redox chemistry of Pyrococcus furiosus rubredoxin and ferredoxin has been studied as a function of temperature in direct voltammetry and in EPR monitored bulk titrations. The E_ms of both proteins, measured with direct voltammetry, have a normal (linear) temperature dependence and show no pH dependence. EPR monitoring is not a reliable method to determine the temperature dependence of the E_m: upon rapid freezing the proteins take their conformation corresponding to the freezing point of the solution.     

Statistical Evaluation of the Effect of Gemfibrosil,a Cholesterol Reducing Drug,on Some Biochemical Coronary Heart Disease Risk Variables

The evaluation is based on the clinic trial with gemfibrosil (“Gevilon”, Parke-Davis) carried out in a group of 48 patients, to whom the drug was administered in the single dose of 900 mg daily during the period of 3 months. In this paper we show the results of the treatment on five biochemical Coronary Heart Disease (CHD) risk variables: Cholesterol (CHOL), High Density Lipoprotein (HDL), Triglyccrides (TGL), Uric Acid (UA) and Glucose (GL). We are concerned with a statistical model allowing to predict which and how large changes in the considered variable can be expected in a patient taking the drug. This is done considering the “regression to the mean” effect.     

Testing the stability of transfer functions

In dendroclimatology, testing the stability of transfer functions using cross-calibration verification (CCV) statistics is a common procedure. However, the frequently used statistics reduction of error (RE) and coefficient of efficiency (CE) merely assess the skill of reconstruction for the validation period, which does not necessarily reflect possibly instable regression parameters. Furthermore, the frequently used rigorous threshold of zero which sharply distinguishes between valid and invalid transfer functions is prone to an underestimation of instability. To overcome these drawbacks, we here introduce a new approach – the Bootstrapped Transfer Function Stability test (BTFS). BTFS relies on bootstrapped estimates of the change of model parameters (intercept, slope, and r²) between calibration and verification period as well as the bootstrapped significance of corresponding models. A comparison of BTFS, CCV and a bootstrapped CCV approach (BCCV) applied to 42,000 pseudo-proxy datasets with known properties revealed that BTFS responded more sensitively to instability compared to CCV and BCCV. BTFS performance was significantly affected by sample size (length of calibration period) and noise (explained variance between predictor and predictand). Nevertheless, BTFS performed superior with respect to the detection of instable transfer functions in comparison to CCV.     

Effect of microbial activity on buried cyanobacterial organic matter

The biomass from which hydrocarbons were formed and the organisms responsible for its production are usually deduced by the use of biochemical markers. In the present study, using a simulated sedimentary system, cyanobacterial organic matter was buried in sediments and exposed to sequential environmental changes ranging from microaerobic conditions at ambient temperature to strongly reducing conditions at a biologically extreme temperature and pressure. Significant changes occurred in the composition of hydrocarbons and fatty acids isolated from the biomass that masked the characteristic patterns exhibited by the original cyanobacterial material. The changes depended on the particular environmental conditions to which the organic matter was exposed. The results stress the need for caution in interpreting biochemical markers in terms of their source material in sediments.     

Continuities in stone flaking technology at Liang Bua, Flores, Indonesia

This study examines trends in stone tool reduction technology at Liang Bua, Flores, Indonesia, where excavations have revealed a stratified artifact sequence spanning 95 k.yr. The reduction sequence practiced throughout the Pleistocene was straightforward and unchanging. Large flakes were produced off-site and carried into the cave where they were reduced centripetally and bifacially by four techniques: freehand, burination, truncation, and bipolar. The locus of technological complexity at Liang Bua was not in knapping products, but in the way techniques were integrated. This reduction sequence persisted across the Pleistocene/Holocene boundary with a minor shift favoring unifacial flaking after 11 ka. Other stone-related changes occurred at the same time, including the first appearance of edge-glossed flakes, a change in raw material selection, and more frequent fire-induced damage to stone artifacts. Later in the Holocene, technological complexity was generated by “adding-on” rectangular-sectioned stone adzes to the reduction sequence. The Pleistocene pattern is directly associated with Homo floresiensis skeletal remains and the Holocene changes correlate with the appearance of Homo sapiens. The one reduction sequence continues across this hominin replacement.     

Remediation of chromite ore processing residue by pyrolysis process with sewage sludge

The present work developed a novel technique to treat chromite ore processing residue (COPR). The process involved mixing the COPR with sewage sludge followed by pyrolysis. The gaseous organic fraction generated during pyrolysis of sludge was beneficial to Cr(VI) reduction. Process variables, such as the amount of sludge added to COPR (sludge-to-COPR (S/C) ratio), heating temperature, reaction time and particle size, were systematically varied, and their influences on the Cr(VI) reduction in COPR were investigated. Cr(VI) content had decreased greatly, from 3384 mg kg⁻¹ for untreated COPR to less than 30 mg kg⁻¹ for COPR treated at 600 °C.     

Microbial transformations of flavanone and 6-hydroxyflavanone by Aspergillus niger strains

Flavanone (1) and 6-hydroxyflavanone (2) were subjected to transformation by means of Aspergillus niger strains (one wild and three UV mutants). For both substrates the biotransformation resulted in reduction of the carbonyl group (products 5 and 7) and dehydrogenation at C-2 and C-3 (3 and 8). Additionally, for flavanone (1) reduction of C-4 together with hydroxylation at C-7 (6) and dehydrogenation at C-2, C-3 along with hydroxylation at C-3 (4) were observed.     

Reduction/pH dual-sensitive PEGylated hyaluronan nanoparticles for targeted doxorubicin delivery

To minimize the side effect of chemotherapy, a novel reduction/pH dual-sensitive drug nanocarrier, based on PEGylated dithiodipropionate dihydrazide (TPH)-modified hyaluronic acid (PEG-SS-HA copolymer), was developed for targeted delivery of doxorubicin (DOX) to hepatocellular carcinoma. The copolymer was synthesized by reductive amination via Schiff's base formation between TPH-modified HA and galactosamine-conjugated poly(ethylene glycol) aldehyde/methoxy poly(ethylene glycol) aldehyde. Conjugation of DOX to PEG-SS-HA copolymer was accomplished through the hydrazone linkage formed between DOX and PEG-SS-HA, and confirmed by FTIR and ¹H NMR spectra. The polymer–DOX conjugate could self-assemble into spherical nanoparticles (∼150 nm), as indicated by TEM and DLS. In vitro release studies showed that the DOX-loaded nanoparticles could release DOX rapidly under the intracellular levels of pH and glutathiose. Cellular uptake experiments demonstrated that the nanoparticles could be efficiently internalized by HepG2 cells. These results indicate that the PEG-SS-HA copolymer holds great potential for targeted intracellular delivery of DOX.     

Activity,Distribution, and Diversity of Sulfate Reducers and Other Bacteria in Sediments above Gas Hydrate (Cascadia Margin,Oregon)

Cold seep environments such as sediments above outcropping hydrate at Hydrate Ridge (Cascadia margin off Oregon) are characterized by methane venting, high sulfide fluxes caused by the anaerobic oxidation of methane, and the presence of chemosynthetic communities. Recent investigations showed that another characteristic feature of cold seeps is the occurrence of methanotrophic archaea, which can be identified by specific biomarker lipids and 16S rDNA analysis. This investigation deals with the diversity and distribution of sulfate-reducing bacteria, some of which are directly involved in the anaerobic oxidation of methane as syntrophic partners of the methanotrophic archaea. The composition and activity of the microbial communities at methane vented and nonvented sediments are compared by quantitative methods including total cell counts, fluorescence in situ hybridization (FISH), bacterial production, enzyme activity, and sulfate reduction rates. Bacteria involved in the degradation of particulate organic carbon (POC) are as active and diverse as at other productive margin sites of similar water depths. The availability of methane supports a two orders of magnitude higher microbial biomass (up to 9.6 2 10 10 cells cm m 3 ) and sulfate reduction rates (up to 8 w mol cm m 3 d m 1 ) in hydrate-bearing sediments, as well as a high bacterial diversity, especially in the group of i -proteobacteria including members of the branches Desulfosarcina/Desulfococcus , Desulforhopalus , Desulfobulbus , and Desulfocapsa . Most of the diversity of sulfate-reducing bacteria in hydrate-bearing sediments comprises seep-endemic clades, which share only low similarities with previously cultured bacteria.     

Biomineralization of Poorly Crystalline Fe(III) Oxides by Dissimilatory Metal Reducing Bacteria (DMRB)

Dissimilatory metal reducing bacteria (DMRB) catalyze the reduction of Fe(III) to Fe(II) in anoxic soils, sediments, and groundwater. Two-line ferrihydrite is a bioavailable Fe(III) oxide form that is exploited by DMRB as a terminal electron acceptor. A wide variety of biomineralization products result from the interaction of DMRB with 2-line ferrihydrite. Here we describe the state of knowledge on the biotransformation of synthetic 2-line ferrihydrite by laboratory cultures of DMRB using select published data and new experimental results. A facultative DMRB is emphasized ( Shewanella putrefaciens ) upon which most of this work has been performed. Key factors controlling the identity of the secondary mineral suite are evaluated including medium composition, electron donor and acceptor concentrations, ferrihydrite aging/recrystallization status, sorbed ions, and co-associated crystalline Fe(III) oxides. It is shown that crystalline ferric (goethite, hematite, lepidocrocite), ferrous (siderite, vivianite), and mixed valence (magnetite, green rust) iron solids are formed in anoxic, circumneutral DMRB incubations. Some products are well rationalized based on thermodynamic considerations, but others appear to result from kinetic pathways driven by ions that inhibit interfacial electron transfer or the precipitation of select phases. The primary factor controlling the nature of the secondary mineral suite appears to be the Fe(II) supply rate and magnitude, and its surface reaction with the residual oxide and other sorbed ions. The common observation of end-product mineral mixtures that are not at global equilibrium indicates that microenvironments surrounding respiring DMRB cells or the reaction-path trajectory (over Eh-pH space) may influence the identity of the final biomineralization suite.